US5426163A - Redispersible powder composed of n-vinylpyrrolidone/vinyl acetate copolymer the preparation and use thereof - Google Patents
Redispersible powder composed of n-vinylpyrrolidone/vinyl acetate copolymer the preparation and use thereof Download PDFInfo
- Publication number
- US5426163A US5426163A US08/314,911 US31491194A US5426163A US 5426163 A US5426163 A US 5426163A US 31491194 A US31491194 A US 31491194A US 5426163 A US5426163 A US 5426163A
- Authority
- US
- United States
- Prior art keywords
- solution
- vinylpyrrolidone
- vinyl acetate
- weight
- dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
- A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/20—Pills, tablets, discs, rods
- A61K9/2004—Excipients; Inactive ingredients
- A61K9/2022—Organic macromolecular compounds
- A61K9/2027—Organic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyvinyl pyrrolidone, poly(meth)acrylates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/20—Pills, tablets, discs, rods
- A61K9/28—Dragees; Coated pills or tablets, e.g. with film or compression coating
- A61K9/2806—Coating materials
- A61K9/2833—Organic macromolecular compounds
- A61K9/284—Organic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyvinyl pyrrolidone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
Definitions
- the present invention relates to a process for preparing a free-flowing redispersible powder composed of a vinylpyrrrolidone (VP)/vinyl acetate (VAc) copolymer which is insoluble in water, to the powder as such and to its use, especially for the controlled release of active substances.
- VP vinylpyrrrolidone
- VAc vinyl acetate
- Vinylpyrrolidone/vinyl acetate solution polymers containing more than 50% by weight of vinyl acetate are insoluble in water and are employed for coatings etc., as solution in organic solvents.
- organic solvents There are well known problems with the use of organic solvents: they are relatively costly, they can be recovered only with difficulty, and usually not at all, and thus pollute the environment, they are a fire and explosion hazard and are also not physiologically acceptable.
- the only alternative to these solution polymers would be the use of the corresponding dispersions.
- 3,244,658, 3,691,125 and 4,167,439 disclose that emulsion polymerizations with vinylpyrrolidone as comonomer (more than 10% by weight of the monomers) result in unstable and highly viscous dispersions which separate and, moreover, are poorly reproducible. Dispersions of this type can be obtained only by grafting vinyl acetate onto vinylpyrrolidone (PVP) introduced into the emulsion polymerization (U.S. Pat. No. 3,691,125). A secondary dispersion of such a copolymer of vinyl esters grafted onto vinylpyrrolidone is described in DE-A 15 44 860.
- the preparation process is very complicated: the graft copolymer is initially hydrolyzed, reacted with diketene, precipitated, washed with water and subsequently dissolved or emulsified in a water-miscible solvent, then dispersed in water and finally the solvent is removed by distillation.
- the resulting graft copolymer is not comparable with a solution polymer of the same comonomers in the same ratio of amounts.
- this object is achieved in that it is possible to prepare a stable secondary dispersion from organic solutions of vinylpyrrolidone/vinyl acetate solution copolymers which are insoluble in water, expediently directly from the polymerization solutions, by addition of one or more surfactants or emulsifiers, with or without protective colloids, and subsequent replacement of the solvent by water, from which dispersion free-flowing readily redispersible powders can be obtained by freeze- or spray-drying.
- the copolymer is prepared in a conventional manner from 15-40, preferably 20-35, % by weight of vinylpyrrolidone and 60-85, preferably 65-80, % by weight of vinyl acetate in an organic solvent (or mixture thereof) with a free radical initiator. It is advantageous to use solution polymers which already have a very low residual monomer content, as are described in U.S. Pat. No. 4,182,851.
- the Fikentscher K value (Cellulose-Chemie 13 (1932) 58-64 and 71-74) of the polymer should be in the range from 16 to 36, preferably 25 to 36, measured in 1 % strength ethanolic solution at 25° C.
- the surfactant is selected according to the requirements for subsequent use of the dispersion from the conventional anionic, cationic or non-ionic surfactants.
- the following surfactants have proven very useful, for example, for use of the dispersion in the pharmaceutical industry: sodium salt of ethylhexyl sulfosuccinate, arylsulfonates, approximately 9-fold ethoxylated stearic acid and sodium lauryl sulfate.
- Suitable protective colloids are all compounds which can be used as such in emulsion polymerization, for example water-soluble cellulose derivatives, gelatin or PVP. They must form either true or colloidal solutions in water.
- Replacement of the solvent can take place, for example, by steam distillation under atmospheric pressure or by stepwise addition of water and subsequent removal of the organic solvent under reduced pressure, and should result in removal of as much of the organic solvent as possible.
- Suitable organic solvents for the polymerization are aliphatic ketones with 3-5 carbon atoms, toluene and, in particular, lower aliphatic alcohols, especially ethanol or isopropanol, or mixtures thereof.
- the secondary dispersion can be dried by freeze-or spray-drying, with or without the addition of spray auxiliaries and antiblocking agents.
- Spray-drying is carried out in a conventional manner in spray towers, it being possible to spray the dispersion in by means of atomizing disks or single- or multi-component nozzles.
- the dispersion is dried with hot gases, eg. with nitrogen or air.
- the spray auxiliaries which are employed are one or more water-soluble substances with a second order phase transition point (glass transition temperature Tg) of at least 60° C., specifically in amounts of from 0 to 50% of the weight of the polymer.
- Particularly suitable spray auxiliaries have proven to be water-soluble polymers, especially those with high degrees of polymerization. Examples which may be mentioned are polyvinyl alcohols, ligninsulfonates, water-soluble condensates of naphthalenesulfonic acid and formaldehyde, polyacrylic acids and polyacrylamides.
- the resulting powder can be mixed with from 0 to 30% by weight, based on the total weight of polymeric components, of antiblocking agents.
- All the antiblocking agents customary for such purposes are suitable, for example colloidal silica, talc, clays and calcium carbonate.
- the redispersible powders obtainable by the process according to the invention can be redispersed simply by stirring with cold water, and the resulting dispersion has essentially the same properties as the secondary dispersion originally obtained on replacement of the solvent as long as there has been no addition of large amounts of auxiliary. They can be used advantageously for example, in the building sector, in the production of paints and coating agents and of glues and adhesives. They have proven particularly useful as binders and coating agents for slow-release pharmaceutical forms with pH-independent control of release of the active substance, and as film-formers for hair spray formulations.
- Solid pharmaceutical forms with controlled release of the active substance by use of polymer are usually marketed as matrix tablets, film-coated tablets or coated pellets or granules with or without a hard gelatin capsule.
- the polymers normally used are cellulose derivatives, shellac or methacrylate copolymers (H. Sucker, P. Fuchs, P. Suiter, Pharmazeutician Technologie, G. Thieme-Verlag Stuttgart, 1978, 349-354). These polymers envelope the active substance, and it is liberated in gastric and/or intestinal fluid by slow diffusion through the polymer and/or erosion of the polymer as a function of the pH or independent thereof.
- One aim in this connection must be to achieve adequate release at the outset in order to reach the minimum concentration of active substance in the blood, and this must be followed by slower release of active substance.
- matrix tablets or granules can be produced by traditional wet granulation of the active substance in a kneader/mixer or by fluidized bed granulation. This entails use of the aqueous dispersion of the powder obtainable according to the invention as binder suspension.
- the pharmaceutical substance can be mixed with the redispersible powder obtainable according to the invention, and this mixture can be granulated with a solvent, preferably water or alcohols, by the abovementioned methods. A combination of the two methods may be worthwhile in some cases. In some circumstances it is advisable to add a filler to the active substance (e.g. lactose, starch, calcium hydrogen phosphate) and/or an anti-stick agent (eg. talc).
- a filler e.g. lactose, starch, calcium hydrogen phosphate
- an anti-stick agent eg. talc
- Pellets can be produced by making a solution or fine dispersion of the active substance in the aqueous dispersion of the powder obtainable according to the invention. Particles of carrier material (eg. sugar beads) are then coated with this dispersion in a conventional manner, eg. in a fluidized bed, until the required amount of active substance has been applied. Another coating of the pellets with the dispersion of the powder obtainable according to the invention without active substance can be applied for additional control of release of active substance from the pellets.
- carrier material eg. sugar beads
- Film-coated tablets according to the invention are produced by applying an aqueous dispersion (or else an organic, preferably alcoholic, solution) of the powder obtainable according to the invention together with the additives customary for tablet coatings (eg. pigments, lacquers, talc) to the cores which contain the active substance in a fluidized bed, coating pan, Accela-Cota or comparable apparatus.
- an aqueous dispersion or else an organic, preferably alcoholic, solution
- the additives customary for tablet coatings eg. pigments, lacquers, talc
- a copolymer of 30% by weight of vinylpyrrolidone and 70% by weight of vinyl acetate prepared by solution polymerization in isopropanol, Fikentscher K value 28 ⁇ 3, measured on a 1% solution of the polymer in ethanol at 25° C.
- the result was a wide dispersion whose solids content was adjusted to 30%.
- the viscosity of the dispersion was 159 mPas, and the residual vinylpyrrolidone and vinyl acetate monomer content was less than 2 ppm of the polymer. Further stabilization of this dispersion was achieved by adding about 1% by weight of 9-fold ethoxylated stearic acid.
- the dispersion was adjusted to a solids content of about 20% and then freeze-dried, and the dried residue was ground to give a fine, free-flowing, non-blocking powder. There was no caking after storage at about 25° C. for several months.
- a copolymer of 30% by weight of vinylpyrrolidone and 70% by weight of vinyl acetate (prepared by solution polymerization in ethanol, K value 32 ⁇ 4, measured as in Example 1), as a 50% strength solution in ethanol was mixed with 0.1% by weight, based on the polymer, of sodium lauryl sulfate and treated as in Example 1.
- the 30% strength dispersion had a viscosity of 4200 mPas. It was diluted to twice the volume with water and then spray-dried.
- the inlet temperature was about 120° C., and the outlet temperature was about 80° C.
- the result was a free-flowing, non-blocking, fine product composed of agglomerated particles of relatively uniform structure. There was no caking after storage at about 25° C. for several months.
- a copolymer of 20% by weight of vinylpyrrolidone and 80% by weight of vinyl acetate prepared by solution polymerization in isopropanol, K value 19 ⁇ 3, measured as in Example 1
- the dispersion was adjusted to 25% by weight and then stabilized by addition of 1% by weight of the sodium salt of ethylhexyl sulfosuccinate. Dilution with water to a solids content of about 15% was followed by spray-drying.
- the inlet temperature was about 105° C. and the outlet temperature was about 70° C.
- the resulting powder had similar properties to that of Example 2.
- the powders obtained as in Examples 1 to 3 were easily dispersible by stirring in cold water.
- the resulting dispersions (whose solids concentration could be adjusted virtually as required) gave on drying uniform films whose transparency and brittleness were virtually the same as those from an organic solution of the solution polymer.
- the minimum film-forming temperature (measured by the DIN 53 787 method) of these dispersions was 14°-17° C.
- Mixture I was granulated with dispersion II in a fluidized bed granulator and was screened, dried, mixed with III and tableted under low compressive force in a rotary tableting machine.
- the release of theophylline was determined by the paddle method of US Pharmacopeia XXII at 50 revolutions per minute.
- a matrix tablet produced in a similar manner with a commercial ethyl acrylate/methyl methacrylate copolymer in place of the vinylpyrrolidone/vinyl acetate copolymer according to the invention was used for comparison.
- the release profiles were very similar to one another but the matrix of Example 1 proved to be more favorable because the release was somewhat higher at the start and somewhat lower later on than with the comparison tablets.
- the redispersible powder according to the invention from Example 1 was used to prepare a dispersion with a solids content of 10% by weight in distilled water. This dispersion was very suitable as a pump spray for hair setting. The film was clear and even without the addition of a flow controller displayed a pleasant gloss. For practical applications merely perfume oils were added.
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Polymers & Plastics (AREA)
- Epidemiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pharmacology & Pharmacy (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Birds (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Medicinal Preparation (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/314,911 US5426163A (en) | 1991-12-04 | 1994-09-19 | Redispersible powder composed of n-vinylpyrrolidone/vinyl acetate copolymer the preparation and use thereof |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4139963A DE4139963A1 (de) | 1991-12-04 | 1991-12-04 | Redispergierbares dispersionspulver aus n-vinylpyrrolidon-vinylacetat-copolymerisat, dessen herstellung und verwendung |
DE4139963.3 | 1991-12-04 | ||
US98341092A | 1992-11-30 | 1992-11-30 | |
US08/314,911 US5426163A (en) | 1991-12-04 | 1994-09-19 | Redispersible powder composed of n-vinylpyrrolidone/vinyl acetate copolymer the preparation and use thereof |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US98341092A Continuation | 1991-12-04 | 1992-11-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
US5426163A true US5426163A (en) | 1995-06-20 |
Family
ID=6446247
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/314,911 Expired - Lifetime US5426163A (en) | 1991-12-04 | 1994-09-19 | Redispersible powder composed of n-vinylpyrrolidone/vinyl acetate copolymer the preparation and use thereof |
Country Status (7)
Country | Link |
---|---|
US (1) | US5426163A (de) |
EP (1) | EP0545209B1 (de) |
JP (1) | JPH05247228A (de) |
AT (1) | ATE140015T1 (de) |
CA (1) | CA2083651C (de) |
DE (2) | DE4139963A1 (de) |
MX (1) | MX9206952A (de) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997031041A1 (en) * | 1996-02-20 | 1997-08-28 | Isp Investments Inc. | Strongly swellable, moderately cross-linked copolymers of vinylpyrrolidone and vinyl acetate |
US5665840A (en) * | 1994-11-18 | 1997-09-09 | Novartis Corporation | Polymeric networks from water-soluble prepolymers |
US5716634A (en) * | 1995-09-13 | 1998-02-10 | Isp Investments Inc. | Clear, homogenized, flowable hydrogel of crosslinked N-vinyl lactam polymer |
US5921055A (en) * | 1996-01-22 | 1999-07-13 | Guardian Fiberglass, Inc. | Method of installing insulation |
US5952418A (en) * | 1995-12-14 | 1999-09-14 | Guardian Fiberglass, Inc. | Fiberglass/dry adhesive mixture and method of applying same in a uniform manner |
US6012263A (en) * | 1996-01-22 | 2000-01-11 | Guardian Fiberglass, Inc. | Method of installing insulation with dry adhesive and/ or cold dye, and reduced amount of anti-static material |
US6047518A (en) * | 1998-08-31 | 2000-04-11 | Guardian Fiberglass, Inc. | Method and apparatus for installing blown-in-place insulation to a prescribed density |
US6107397A (en) * | 1997-03-24 | 2000-08-22 | Basf Aktiengesellschaft | Aqueous copolymer dispersions of water-soluble monomers with N-vinyl groups and hydrophobic monomers |
WO2002077075A1 (fr) * | 2001-03-22 | 2002-10-03 | Rhodia Chimie | Procede de fabrication de particules colloidales de forme controlee avec des copolymeres a blocs hydrosolubles comprenant un bloc hydrophobe et un bloc hydrophile |
WO2003014168A1 (en) * | 2001-08-08 | 2003-02-20 | Isp Investments Inc. | Aqueous dispersions of low-molecular weight, low-melting and water insoluble polymers |
US6743763B1 (en) * | 2000-09-05 | 2004-06-01 | Basf Corporation | Stable aqueous laundry detergents containing vinyl pyrrolidone copolymers |
US20040139625A1 (en) * | 2003-01-08 | 2004-07-22 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for preparing vinylpyrrolidone polymer powder |
US20050131054A1 (en) * | 2002-03-25 | 2005-06-16 | Joerg Breitenbach | Test system for evaluating the compatibility of biologically active substances with copolymers |
US20060122321A1 (en) * | 2004-12-07 | 2006-06-08 | Basf Aktiengesellschaft | Method of producing aqueous secondary dispersions of water-insoluble polymers |
US20060205616A1 (en) * | 2005-03-09 | 2006-09-14 | Alberto-Culver Company | Sustained-release fragrance delivery system |
US20060240102A1 (en) * | 2005-04-20 | 2006-10-26 | Basf Aktiengesellschaft | Binders for tablets with high strength based on finely divided vinyllactam polymers, the production and use thereof |
CN100439423C (zh) * | 2005-07-08 | 2008-12-03 | 第一工业制药株式会社 | 低休止角粉末状乙烯基吡咯烷酮聚合物及其制造方法 |
US20100113666A1 (en) * | 2007-01-19 | 2010-05-06 | Rhodia Services | Diblock copolymer including units derived from styrene and units derived from acrylic acid |
US20110046072A1 (en) * | 2008-05-07 | 2011-02-24 | Bayer Animal Health Gmbh | Solid pharmaceutical formulation with delayed release |
CN104870397A (zh) * | 2012-12-14 | 2015-08-26 | 陶氏环球技术有限责任公司 | 液压凝固混合物的添加剂 |
US10022328B2 (en) | 2015-02-20 | 2018-07-17 | Cytec Industries Inc. | Dialkyl sulfosuccinate compositions, method of making, and method of use |
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DE4306808A1 (de) * | 1993-03-04 | 1994-09-08 | Wacker Chemie Gmbh | Vernetzbare Dispersionspulver als Bindemittel für Fasern |
DE69534647T2 (de) * | 1994-09-19 | 2006-07-27 | Sekisui Kagaku Kogyo K.K. | Behälter und träger für die blutuntersuchung enthaltend einen blutkomponenten adhäsions-inhibitor |
DE4438706A1 (de) * | 1994-10-29 | 1996-05-02 | Basf Ag | Lösliche Copolymerisate für die Haarkosmetik |
DE19814730A1 (de) * | 1998-04-02 | 1999-10-07 | Basf Ag | Verwendung von N-Vinyllacram oder N-Vinylamin haltigen Copolymeren als Matrix zur Herstellung von festen pharmazeutischen und kosmetischen Darreichungsformen |
DE19836646A1 (de) * | 1998-08-13 | 2000-02-17 | Basf Ag | Verwendung von N-Vinylpyrrolidon- und Vinylacetat-haltigen Copolymeren als Matrix zur Herstellung von festen, oralen pharmazeutischen und kosmetischen Zubereitungen |
AT413647B (de) * | 1998-11-26 | 2006-04-15 | Sandoz Ag | Verwendung eines copolymerisats aus 1-vinyl-2-pyrrolidon und vinylacetat zur herstellung von cefuroximaxetil-hältigen tabletten |
FR2819719B1 (fr) * | 2001-01-19 | 2005-04-29 | Snf Sa | Nouvelles compositions epaissies et transparentes, comportant au moins un polymere epaississant en poudre traitee par lavage/filtration/sechage, et leurs applications cosmetiques, pharmaceutiques, industrielles |
WO2011086194A1 (en) | 2010-01-18 | 2011-07-21 | Cephalon France | Improved oral lysophilisates containing pvp/va |
DE102010039380A1 (de) | 2010-08-17 | 2012-02-23 | Henkel Ag & Co. Kgaa | Mattierungsadditiv für Blondierungen |
KR102370310B1 (ko) * | 2014-02-19 | 2022-03-04 | 바스프 에스이 | 용융 필라멘트 압출 조형에 사용하기 위한 지지체 재료로서의 폴리머 |
CN112691187B (zh) * | 2020-12-30 | 2021-12-21 | 深圳新发源植物科技发展有限公司 | 一种用于防止额前脱发的缓释膜及其制备方法 |
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US3244658A (en) * | 1960-11-16 | 1966-04-05 | Gen Aniline & Film Corp | Process of preparing a stable aqueous emulsion |
DE1544860A1 (de) * | 1963-02-16 | 1969-06-26 | Hoechst Ag | Verfahren zur Herstellung von stabilen Polyvinylacetessigesterdispersionen |
US3691125A (en) * | 1970-05-04 | 1972-09-12 | Gaf Corp | Stable aqueous emulsions |
US4053696A (en) * | 1974-11-30 | 1977-10-11 | Basf Aktiengesellschaft | Manufacture of vinylpyrrolidone polymers |
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US4182851A (en) * | 1977-07-02 | 1980-01-08 | Basf Aktiengesellschaft | Process for reducing the residual monomer content in the polymerization of vinyl-lactams and vinyl esters |
US4520179A (en) * | 1982-09-20 | 1985-05-28 | Gaf Corporation | Preparation of vinylpyrrolidone/vinyl acetate copolymers of various molecular weights using a single initiator system consisting essentially of t-Butylperoxypivalate |
US4906701A (en) * | 1986-12-09 | 1990-03-06 | Phillips Petroleum Company | Inverse emulsion polymerization |
US5077040A (en) * | 1990-04-30 | 1991-12-31 | Helene Curtis, Inc. | Hair-treating microemulsion composition and method of preparing and using the same |
US5122582A (en) * | 1989-09-22 | 1992-06-16 | Basf Aktiengesellschaft | Preparation of copolymers which form clear aqueous solutions |
-
1991
- 1991-12-04 DE DE4139963A patent/DE4139963A1/de not_active Withdrawn
-
1992
- 1992-11-24 AT AT92119930T patent/ATE140015T1/de not_active IP Right Cessation
- 1992-11-24 CA CA002083651A patent/CA2083651C/en not_active Expired - Fee Related
- 1992-11-24 DE DE59206699T patent/DE59206699D1/de not_active Expired - Fee Related
- 1992-11-24 EP EP92119930A patent/EP0545209B1/de not_active Expired - Lifetime
- 1992-12-01 JP JP4321766A patent/JPH05247228A/ja not_active Withdrawn
- 1992-12-02 MX MX9206952A patent/MX9206952A/es unknown
-
1994
- 1994-09-19 US US08/314,911 patent/US5426163A/en not_active Expired - Lifetime
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US5952418A (en) * | 1995-12-14 | 1999-09-14 | Guardian Fiberglass, Inc. | Fiberglass/dry adhesive mixture and method of applying same in a uniform manner |
US5921055A (en) * | 1996-01-22 | 1999-07-13 | Guardian Fiberglass, Inc. | Method of installing insulation |
US6012263A (en) * | 1996-01-22 | 2000-01-11 | Guardian Fiberglass, Inc. | Method of installing insulation with dry adhesive and/ or cold dye, and reduced amount of anti-static material |
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US6107397A (en) * | 1997-03-24 | 2000-08-22 | Basf Aktiengesellschaft | Aqueous copolymer dispersions of water-soluble monomers with N-vinyl groups and hydrophobic monomers |
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US6829843B2 (en) | 2003-01-08 | 2004-12-14 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for preparing vinylpyrrolidone polymer powder |
US8003738B2 (en) | 2004-12-07 | 2011-08-23 | Basf Se | Method of producing aqueous secondary dispersions of water-insoluble polymers |
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US20060205616A1 (en) * | 2005-03-09 | 2006-09-14 | Alberto-Culver Company | Sustained-release fragrance delivery system |
US7638477B2 (en) | 2005-03-09 | 2009-12-29 | Alberto-Culver Company | Sustained-release fragrance delivery system |
US20060240102A1 (en) * | 2005-04-20 | 2006-10-26 | Basf Aktiengesellschaft | Binders for tablets with high strength based on finely divided vinyllactam polymers, the production and use thereof |
US8268350B2 (en) | 2005-04-20 | 2012-09-18 | Basf Se | Binders for tablets with high strength based on finely divided vinyllactam polymers, the production and use thereof |
CN100439423C (zh) * | 2005-07-08 | 2008-12-03 | 第一工业制药株式会社 | 低休止角粉末状乙烯基吡咯烷酮聚合物及其制造方法 |
US20100113666A1 (en) * | 2007-01-19 | 2010-05-06 | Rhodia Services | Diblock copolymer including units derived from styrene and units derived from acrylic acid |
US20110046072A1 (en) * | 2008-05-07 | 2011-02-24 | Bayer Animal Health Gmbh | Solid pharmaceutical formulation with delayed release |
CN104870397A (zh) * | 2012-12-14 | 2015-08-26 | 陶氏环球技术有限责任公司 | 液压凝固混合物的添加剂 |
US20150307399A1 (en) * | 2012-12-14 | 2015-10-29 | Dow Global Technologies Llc | Additive for hydraulically setting mixtures |
US10022328B2 (en) | 2015-02-20 | 2018-07-17 | Cytec Industries Inc. | Dialkyl sulfosuccinate compositions, method of making, and method of use |
Also Published As
Publication number | Publication date |
---|---|
CA2083651C (en) | 2004-08-24 |
ATE140015T1 (de) | 1996-07-15 |
JPH05247228A (ja) | 1993-09-24 |
DE4139963A1 (de) | 1993-06-09 |
MX9206952A (es) | 1993-06-01 |
EP0545209A1 (de) | 1993-06-09 |
EP0545209B1 (de) | 1996-07-03 |
DE59206699D1 (de) | 1996-08-08 |
CA2083651A1 (en) | 1993-06-05 |
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